EP0609079B1 - Process for producing liquid and, optionally gaseous products from gaseous reactants - Google Patents
Process for producing liquid and, optionally gaseous products from gaseous reactants Download PDFInfo
- Publication number
- EP0609079B1 EP0609079B1 EP94300600A EP94300600A EP0609079B1 EP 0609079 B1 EP0609079 B1 EP 0609079B1 EP 94300600 A EP94300600 A EP 94300600A EP 94300600 A EP94300600 A EP 94300600A EP 0609079 B1 EP0609079 B1 EP 0609079B1
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- EP
- European Patent Office
- Prior art keywords
- vessel
- backflushing
- liquid product
- liquid
- gaseous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/34—Apparatus, reactors
- C10G2/342—Apparatus, reactors with moving solid catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/006—Separating solid material from the gas/liquid stream by filtration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0405—Apparatus
- C07C1/041—Reactors
- C07C1/0415—Reactors with moving catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0455—Reaction conditions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/06—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen in the presence of organic compounds, e.g. hydrocarbons
- C07C1/063—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen in the presence of organic compounds, e.g. hydrocarbons the organic compound being the catalyst or a part of the catalyst system
- C07C1/066—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen in the presence of organic compounds, e.g. hydrocarbons the organic compound being the catalyst or a part of the catalyst system used for dissolving, suspending or transporting the catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00103—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor in a heat exchanger separate from the reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00105—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling
- B01J2219/0011—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling involving reactant liquids
Definitions
- THIS INVENTION relates to a process for producing liquid and, optionally, gaseous products from gaseous reactants. It relates also to an installation for producing liquid and, optionally, gaseous products from gaseous reactants.
- WO-A-93/16796 discloses a slurry reactor containing an internal filtering unit. A pressure differential exists accross the filtering membrane and pressure flucctuations are imposed. The magnitude of the pressure fluctuations may be such, that some backflushing will occur.
- the solid particles will normally be catalyst particles for catalyzing the reaction of the gaseous reactants into the liquid product, and, when applicable, the gaseous product; and the suspension liquid will normally, but not necessarily always, be the liquid product.
- the process can have broader application, it is envisaged that it will have particular application in hydrocarbon synthesis where the gaseous reactants are capable of reacting catalytically in the slurry bed to form liquid hydrocarbon product and, optionally, gaseous hydrocarbon product.
- the hydrocarbon synthesis may be Fischer-Tropsch synthesis, with the gaseous reactants being in the form of a synthesis gas stream comprising mainly carbon monoxide and hydrogen, and with both liquid and gaseous hydrocarbon products being produced.
- the catalyst particles can thus be any desired Fischer-Tropsch catalyst, such as an iron-based catalyst, a cobalt-based catalyst, or any other Fischer-Tropsch catalyst.
- the catalyst particles may have a desired particle size range, eg no particles greater than 300 microns and less than 5% by mass of the particles being smaller than 22 microns.
- the catalyst particle size range may be selected, bearing in mind the filtering medium.
- the filtering medium may be selected bearing in mind the catalyst particle size range.
- the slurry bed can thus be provided in a suitable vessel, with unreacted reactants and gaseous product being withdrawn from the vessel above the slurry bed, and the separated liquid product also being withdrawn from the vessel.
- the vessel will thus be maintained at normal elevated pressure and temperature conditions associated with Fischer-Tropsch synthesis, eg a predetermined operating pressure in the range 18 to 50 bar, and at a predetermined temperature in the range 160°C and 280°C, or even higher for the production of lower boiling point product.
- the slurry bed may be characterized thereby that it, and in particular the filtration zone thereof, is not mechanically mixed or agitated, eg not mechanically stirred.
- the catalyst particles in the slurry bed, and in particular in the filtration zone thereof, are thus maintained in suspension by the turbulence created by the synthesis gas stream passing through the slurry bed, ie bubbling through the bed.
- the gas velocity through the slurry bed is thus sufficiently high to maintain the slurry bed, and in particular the filtration zone thereof, in a state of turbulence or suspension.
- the superficial gas velocity through the filtration zone may be between 5 and 70 cm/s, typically between 15 and 55 cm/s, based on the filtration zone open cross-sectional area.
- the filtering medium may be part of a filter cartridge or element mounted in the vessel, and may be of a type which is of elongate form, with the filtering medium being of cylindrical form and enclosing a filtrate collecting zone, and with a filtrate outlet for withdrawing filtrate, ie liquid product, being provided at one end thereof.
- the filtering medium can be any desired filtering medium having a desired opening size to prevent catalyst particles passing therethrough, it is preferably of a type with which permanent clogging or impregnation thereof with the catalyst particles does not occur.
- the filtering medium can be a mesh, porous material such as ceramic, perforated sheet, spiral wire wound, eg from wedge wire, or the like.
- the filter elements may be located at the same or different levels within the filtration zone. Preferably a number of the filter elements are located close to the upper surface of the slurry bed, ie the filtration zone is provided close to the upper surface of the slurry bed.
- the filter elements may be arranged in a plurality of banks, with each filter bank comprising a number of the filter elements.
- the elements can be located at any desired inclination; however, they are preferably located vertically with their liquid product or filtrate outlets directed downwardly.
- the passage of the liquid product through the filtering media may be effected by applying a pressure differential across the filtering media and any cake build-up thereon.
- this pressure differential may be up to 8 bar, and is typically in the region of about 4 bar.
- the pressure differential may be effected by withdrawing the liquid product into a rundown vessel which is at a lower pressure than the reactor vessel, with the filtrate outlets of the filter elements being connected to the rundown vessel by means of suitable liquid product conduits.
- the conduits may include a primary liquid product conduit leading from the filtrate outlet of each filter element; a secondary liquid product conduit into which the primary conduits of all the filter elements of the particular bank of filter elements tie; and a tertiary liquid product conduit leading to the rundown vessel, with the secondary conduits all tying into the tertiary conduit.
- the flushing fluid may be process or non-process derived liquid and/or gas, eg some of the liquid and/or gaseous product.
- the backflushing may, in general, be effected in pulse-like fashion.
- the backflushing may comprise an initial pulse of flushing liquid and/or gas, optimally followed by one or more further pulses of flushing liquid and/or gas.
- Each backflushing pulse may comprise initiating backflushing rapidly, ie commencing flow of flushing fluid rapidly; and backflushing the elements rapidly with a volume of the flushing fluid.
- This volume of flushing fluid may be relatively large, eg approximately equivalent to the internal volume of the filter elements. It can, however, be less than the internal volume of the filter elements, eg less than half their internal volume.
- the volume of flushing fluid used during a second pulse may be less than that of the initial pulse, eg less than half the internal volume of the elements.
- the volume of flushing fluid used during a further or second pulse may be similar to that of the initial pulse.
- the nature of any further pulses, when utilized, and the volume of the flushing fluid used during such pulses, may be similar to those of the second pulse hereinbefore described.
- the pressure differential across the filtering media and filter cake during backflushing may be up to 10 bar depending on the degree of clogging or age of the filtering media, and is typically in the region of 5 bar.
- the flushing fluid flow rate may be at least 6000 l/h/m 2 of filtering media.
- the flushing fluid flow rate may be between 6000 l/h/m 2 of filtering media when the pressure differential across the filtering media is about 5 bar, and between about 10000 and 12000 l/h/m 2 when the pressure differential is about 10 bar.
- the waiting period during which no filtering or backflushing takes place ie during which there is no liquid flow through the filtering media of the elements, to enhance subsequent filtration, may be between 15 and 60 minutes, or even longer, but is typically about 30 minutes.
- the liquid product conduits and rundown vessel may conveniently form part of the backflushing means, with the rundown vessel then also constituting a flushing fluid vessel and the liquid product conduits constituting flushing fluid conduits; however, if desired, a separate flushing fluid vessel and flushing fluid conduit leading from the flushing fluid vessel to the secondary conduits, may be provided.
- the backflushing means may include at least one quick opening valve or the like, for effecting the backflushing pulses, in one of the flushing conduits; and pressurizing means for pressurizing the flushing fluid vessel.
- backflushing may be effected by pressurizing the flushing fluid vessel with the vessel containing some flushing liquid and/or gas, which may be product, and then actuating the quick opening valve until the desired volume of flushing liquid and/or gas has passed through the filter elements of a bank of the filter elements in the second direction.
- a pump and/or compressor can be used for supplying the flushing fluid to the filter elements.
- backflushing may be effected by propelling or forcing residual liquid product in the conduits back through the filter elements in the second direction, preferably also through a restriction orifice located in the primary conduit of each filter element, by means of pressurized gas. It has been found that cleaning of the filter element surfaces is considerably improved, thus enhancing subsequent filtering performance thereof, when backflushing with the gas is effected for at least a sufficiently long period of time to displace substantially all the residual liquid product through the restriction orifices back into the filter elements.
- Backflushing with gas also has the advantage that the gas thereby introduced into the reactor vessel and which is removed with the product gas, does not have to be filtered again, thereby reducing loading on the filter elements during filtration.
- reference numeral 10 generally indicates an installation according to one embodiment of the invention, for producing gaseous and liquid products from gaseous reactants.
- the installation 10 includes an upright cylindrical Fischer-Tropsch synthesis reactor vessel 12.
- the vessel 12 provides a slurry bed zone normally containing a slurry bed 14 of catalyst particles suspended in liquid product and through which gas is passing, as described in more detail hereunder.
- the slurry bed 14 has an upper surface 16, and the expanded height of the slurry bed 14 while gas passes through it is typically between 14 and 18 m when the total reactor length is about 24 m.
- a synthesis gas flow line or conduit 18 is connected to a gas inlet (not shown) provided at the bottom of the vessel 12, while a gas withdrawal flow line or conduit 20 leads from a gas outlet (not shown) provided at the top of the vessel 12.
- a suitable gas distributor (not shown) is connected to the gas inlet.
- the installation 10 also includes a plurality of filter elements 30 (only some of which are shown) located in a filtration zone 22 within the slurry bed 14, arranged in a plurality of banks.
- Each filter element 30 is of elongate cylindrical form, and comprises a cylindrical filtering medium 32 enclosing a filtrate or liquid collecting zone 33.
- the medium 32 is located between end plates 34, 36.
- a mounting rod 38 protrudes from the end plate 34, while a flanged liquid outlet 40 is provided on the end plate 36.
- filtrate or liquid can be withdrawn from the collecting zone of the element or cartridge 30.
- the elements 30 are mounted in position in the vessel 12 by means of the rod 38 and flanged outlets 40. This mounting is not shown in detail in the drawings, but is typically effected by connecting the rod 38 to a lattice or grid spanning the vessel 12, while the outlet is connected to a conduit as hereinafter described.
- the filtering medium 32 comprises a spiral wound wire 42 embedded in, or attached to, circumferentially spaced elongate supports 44 extending between the end plates 34, 36. Filtration openings or slots 46 are thus provided between adjacent loops of the wire 42.
- the wire 42 has, adjacent the openings or slots 46, surfaces 47 which taper away from each other, in the direction of the collecting zone.
- the wire 42 thus also has surfaces 48 against which a cake of catalyst particles (not shown) will form, as described in more detail hereunder, when liquid product is filtered by the elements 30 as it passes through the slots 46 in the direction of arrow 49.
- solid particles will not readily permanently clog or impregnate the openings or slots 46 when filtered product passes through in the direction of arrow 49.
- the filter elements 30 have an external diameter of 11 to 12 cm, with the wire 42 being of stainless steel.
- the wire 42 is typically about 1,2 mm wide at its base.
- the width of the slots or openings 46 is typically between 0,02-0,04 mm.
- any other suitable elongate filter elements or cartridges such as ceramic or sintered metal filter elements, can be used.
- the filtration zone 22 is preferably located at a high level within the slurry bed, so that the filter elements 30 are located near the upper surface 16 thereof. As a result, they will not be embedded in settled solids or catalyst on slumping of the bed 14 which will occur if the gas feed to the vessel 12 is interrupted. However, it has been found that the filtration zone 22 need not necessarily be located near the top of the slurry bed 14 but can instead be located lower down since, should such bed slump occur, it has been found permanent clogging of the filter elements 30 will still not readily occur even if the elements are completely surrounded by settled solids or catalyst.
- the elements 30 are preferably located with their outlets 40 directed downwardly so that any solid or catalyst fines which pass through the slots 46 with the filtrate (liquid product) will tend to collect in the bottom of the collection zones of the filter elements 30 from where they will be washed out with the liquid product.
- a primary conduit 51 To the outlet 40 of each of the filter elements 30 is connected a primary conduit 51, fitted with a restriction orifice 50.
- the conduits 51 of all the filter elements 30 making up a bank of the elements tie into a common secondary conduit 53 fitted with a shut-off valve 52. All the conduits 53 tie into a common tertiary conduit 54, fitted with a quick opening valve 56.
- a conduit 55 leads from the conduit 54 and is fitted with a shut-off or isolation valve 58.
- the conduit 55 leads into the top of a liquid blowdown vessel 60.
- a liquid rundown conduit 62, fitted with a shut-off valve 64 leads from the bottom of the vessel 60.
- the conduit 55 also serves as a backflushing conduit for gas.
- a liquid backflush conduit 66 fitted with a shut-off valve 68, can lead from the conduit 62, upstream of the valve 64, back to the conduit 54, between the valves 56, 58.
- a pressurizing gas conduit or line 70, fitted with a control valve 72 leads into the top of the vessel 60, while a vent conduit or line 74, fitted with a control valve 76, leads from the top of the vessel 60.
- synthesis gas comprising mainly carbon monoxide and hydrogen
- the gas flow rate to the vessel 12 is such as to give a superficial gas velocity in the filtration zone 22, based on the open cross-sectional area of the filtration zone, of between 5 and 70 cm/s, typically about 30 to 40 cm/s.
- the slurry bed 14 is maintained.
- the slurry bed 14 comprises catalyst particles suspended in liquid product, ie liquid wax produced in the vessel 12 on reaction of the gaseous reactants.
- the catalyst particles are maintained in suspended state in the slurry bed 14, and in particular in the filtration zone 22, only by means of the turbulence created therein by the gas passing upwardly therethrough. This turbulence also inhibits excessive cake build-up on the filtering media, and thus enhances filtration through the media.
- the catalyst can be any suitable Fischer-Tropsch synthesis catalyst, and can typically be an iron-based catalyst prepared by precipitation and spray-drying.
- the catalyst particle size distribution is such typically that there are no particles larger than 300 microns, while the fraction of particles smaller than 22 microns is typically less than 5% by volume of the catalyst loaded into the reactor vessel 12.
- the proportion of small particles, ie particles smaller than 22 microns should be as low as possible, up to 40% by volume of such particles, based on total catalyst volume, can be tolerated. It has further been found that higher filtration rates are achievable when the content of particles smaller than 5 microns is minimized.
- the vessel 12 is typically maintained at an operating pressure of about 20 bar, and at an operating temperature between 180°C and 260°C, typically about 240°C.
- the operating pressure can be in excess of 20 bar, and the operating temperature higher or lower than 240°C, as hereinbefore described, depending on the nature and spread of gaseous and liquid products required and the type of catalyst used.
- the vessel 12 will be provided with suitable temperature control means, such as cooling coils for controlling the reaction temperatures, as well as suitable pressure control means such as a pressure control valve.
- the carbon monoxide and hydrogen react to form a range of products in accordance with known Fischer-Tropsch reactions. Some of these products are in gaseous form at the operating conditions of the vessel 12 and are withdrawn, together with unreacted synthesis gas, along the flow line 20. Some of the products produced, such as the waxes already mentioned, are in liquid form at the operating conditions of the vessel 12, and act as the suspension medium for the catalyst particles. As liquid product is formed, the level 16 of the slurry bed naturally rises, and the liquid product is thus withdrawn in the filtration zone by means of the filter elements 30 and rundown vessel 60 to maintain the slurry bed level. This internal filtration constitutes a first stage of the operating cycle of the filter elements 30.
- the vessel 60 is maintained, by means of pressurizing gas introduced along the line 70, at elevated pressure, which is, however, lower than that in the vessel 12.
- the pressure in the vessel 60 is set such that the pressure differential across the filtering media of the elements 30 and any filter cake build-up thereon, is about 4 bar.
- the filter cake when it has built up to some thickness, it must then be backflushed from the filtering media, in a second stage of the operating cycle of the filter elements 30.
- the backflushing is effected by shutting the quick opening valve 56 and valve 58, and withdrawing at least some of the liquid product in the rundown vessel 60, through the flow line 62, in order to remove any solids which have settled out in the bottom of the vessel 60.
- the pressure in the vessel 60 is then increased, by means of the gas pressurizing line 70, to a pressure greater than the operating pressure in the vessel 12.
- the liquid pressure at the quick opening valve 56 is typically slightly lower than the pressure in the vessel 60, but still sufficient for backflushing.
- the vessel 60 will thus contain some liquid product; however, if it is desired to backflush with gas, the vessel 60 will be pressurized with gas only, which can then be gaseous product such as tail gas.
- Backflushing is effected in pulse-like fashion on one bank of filter elements 30 at a time, using either liquid product or gas.
- one of the valves 52 will be open, with the remaining valves 52 closed.
- valve 68 will be open, while for backflushing with gas, valve 58 will be open.
- the quick opening valve 56 is opened rapidly in less than 0,8 seconds, and a volume of liquid product or gas, approximately equivalent to the internal volume of the filter elements 30 making up the bank of elements being flushed, is allowed to pass from the vessel 60, to produce a flow through the backflushing conduit 66 or 55, and the conduits 54, 53 and 51, thereby to provide flushing fluid through the bank of elements 30, in a second direction opposite to the direction in which the product flows during filtering. This typically takes up to 30 seconds. Thereafter, the quick opening valve 56 is again shut.
- the vessel 60 is then again repressurized.
- the quick opening valve 56 is again opened rapidly for a second time. This time a flushing fluid volume equivalent to about one-third of the volume in the first backflushing operation, is allowed to pass from the vessel 60 to the filter elements 30.
- the valve 56 is thereafter again closed. If desired, at least one further similar backflushing step can be effected on that particular bank or filter elements.
- rapid backflushing may be effected by using pressurized gas, which forces residual liquid product in the conduits through the filter elements in the second direction.
- backflushing is then effected at least until backflushing gas starts passing through the restriction orifices.
- any gas which has collected in the elements 30, is displaced by the backflushing fluid and some dislodging of the filter cake from the filtering media may be effected.
- dislodging and breaking up of the filter cake from the media by hydraulic action is primarily effected.
- the flow rate of flushing fluid, during the first and second backflushing steps, is typically between 6000 and 9000 l/h/m 2 of filtering medium at a pressure differential of about 5 bar, and between 10000 and 12000 l/h/m 2 of filtering media at a pressure differential of about 10 bar, as hereinbefore described.
- the flow and distribution of the flushing fluid to the filter elements 30 of the bank of elements being flushed is regulated by means of the restriction orifices 50, which typically have orifice sizes of about 7,5 mm, but the actual size depends on the flow per element and the number of elements per bank.
- the restriction orifices 50 thus serve to distribute the backflushing fluid evenly between the filter elements 30 of the bank being flushed.
- each bank of filter elements 30 Thereafter, in a third stage of the operating cycle of each bank of filter elements 30, they are subjected to a waiting period in which no liquid passes through them.
- the Applicant has found that the filtration rate, when the filter elements 30 are then thereafter again subjected to filtration as hereinbefore described, increases with an increase in the duration of the waiting or non-active period. However, this must be balanced against the disadvantage that the filter elements are out of service during these waiting times. It has been found that a waiting period of between 15 and 30 minutes gives good results.
- gas is vented from the rundown vessel 60 by means of the line 74, in order to return the vessel 60 to the pressure required for the subsequent filtering operation.
- the slurry bed 14 can be maintained at relatively constant levels for prolonged periods of continuous operation.
- the vessel 12 could operate reliably for several months with no permanent clogging of the filter elements 30 or mechanical failure thereof occurring. It may, however, be necessary to withdraw some slurry from time to time, and to add fresh catalyst, eg to maintain catalyst activity.
- reference numeral 100 generally indicates an installation according to another embodiment of the invention, for producing gaseous and liquid products from gaseous reactants.
- each conduit 53 is provided with one of the quick opening valves 56, while the pressurizing conduit 70 for the vessel 60, and the backflush conduit 66 are dispensed with.
- each of the conduits 53 is in the form of a loop, with the valve 56 provided near one end of the loops, and valves 102, 104, which are similar to the valves 52, 56 respectively, near another end of the loop.
- the conduits 53 also tie into a common backflush fluid conduit 106, which leads from a backflush fluid vessel 110, and is fitted with a valve 108.
- a gas pressurizing line 112, fitted with a valve 114, leads into the vessel 110, as does a backflush liquid feed line 116, fitted with a valve 118.
- the vessel 110 is supplied, by means of the flow line 116, with backflush liquid which can be, but is not limited to, filtered wax from the vessel 60.
- backflush liquid which can be, but is not limited to, filtered wax from the vessel 60.
- the pressure in the vessel 110 is maintained at a pressure which is preferably at least 5 bar higher than the pressure in the reactor vessel 12 by means of gas introduced along the flow line 112.
- the rate at which gas is introduced is preferably sufficient to prevent a drop in pressure in the vessel 110 of more than 1 bar during backflushing.
- Backflushing is effected on one bank of filter elements 30 while maintaining filtration through the remaining banks, by closing the filtration valve 56 of that bank. This is followed by rapid opening, preferably in less than 1 second, of the backflush valve 104 of that bank of elements.
- the backflush valve 104 remains open for a period which is sufficient for the required volume of backflush fluid to flow out of the backflush vessel 110 along the conduit 106, and is thereafter closed.
- the backflushing can be repeated on the same filter bank, or on the next bank of element by opening and closing the required filtering valves 56, and opening the appropriate backflush valve 104.
- a pump 120 fitted with a controlled kickback loop, for liquid backflush, or a compressor (not shown) for gas backflush, can be used, as indicated in broken line in Figure 5.
- the withdrawn slurry can be subjected to external decantation, ie the solids allowed to settle under quiescent conditions, and the resultant clarified liquid product decanted.
- decantation is slow, requires large high pressure vessels which need to be operated isothermally to prevent remixing due to convection, separation is usually incomplete, pumps are required, capital costs are high, and a large catalyst inventory is required.
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- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
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Abstract
Description
- slurry and catalyst handling and transfer systems and equipment in the form of pipes, pumps and tanks are largely eliminated, since the filter cakes are formed on the filter elements inside the reactor and, on backflushing, are directly dispersed back into the slurry bed of the reactor;
- the re-slurrying of the filter cake, which requires some effort, is easily effected through the natural turbulence present in the slurry bed in the reactor, as a result of the gas bubbling through the slurry bed;
- the
filter elements 30 and filter cakes are at all times kept at process conditions which, in theslurry bed 14, are practically isothermal; - in the known reactors, should there be unplanned
shut-downs, slurries and high melting point
liquids (waxes) in external filtration equipment
can easily solidify on cooling, causing
blockages; in the
installations reactor vessel 12 at a sufficiently high temperature to prevent such cooling down, or to drain it, thereby substantially reducing the risk of blockages of filters; - in the
installations internal filter elements 30 occurs frequently enough to prevent excessive build-up, and hence temporary "loss", of catalyst in the filter cake; - the catalyst in the filter cakes in the
installations - being able to minimize the period that liquid
products are kept external to the reactor at the
high temperature prevailing in the
reactor 12 and which could otherwise lead to a deterioration of liquid product quality if subjected to these high temperatures for longer periods.
Claims (22)
- A process for producing liquid and, optionally, gaseous products from gaseous reactants, characterized in that the process comprisesfeeding gaseous reactants at a low level into a slurry bed of solid particles suspended in a suspension liquid;allowing the gaseous reactants to react as they pass upwardly through the slurry bed, thereby to form liquid and, optionally, gaseous products;separating liquid product from the solid particles by passing, in a filtration zone within the slurry bed, liquid product through a filtration medium in a first direction, so that a cake of the solid particles forms on the filtration medium;interrupting the passage of liquid product through the filtering medium;backflushing the filtering medium by passing a flushing fluid through the filtering medium in a second direction, opposite to the first direction, for at least a portion of the period that the liquid product passage is interrupted, thereby to dislodge the cake from the filtering medium;subjecting the filtering medium to a waiting period during which no filtering or backflushing therethrough takes place, to enhance removal of the filter cake as a result of turbulence within the slurry bed; andagain passing liquid hydrocarbon product through the filtering medium in the first direction so that a cake of solid catalyst particles again forms on the filtering medium.
- A process according to Claim 1, characterized in that the solid particles are catalyst particles for catalyzing the reaction of the gaseous reactants into the liquid product, and, when applicable, the gaseous product.
- A process according to Claim 2, characterized in that the gaseous reactants are in the form of a synthesis gas stream comprising mainly carbon monoxide and hydrogen, with the gaseous reactants reacting in accordance with Fischer-Tropsch synthesis reactions, and with both liquid and gaseous hydrocarbon products being produced.
- A process according to Claim 2 or Claim 3, characterized in that the slurry bed is provided in a reactor vessel, with unreacted reactants and any gaseous product being withdrawn from the vessel above the slurry bed, and the separated liquid product also being withdrawn from the vessel, the slurry bed being characterized thereby that at least its filtration zone is not mechanically mixed, with the catalyst particles in at least the filtration zone of the slurry bed thus being maintained in suspension by the turbulence created by the gaseous reactants passing through the slurry bed, and with the gas velocity through the slurry bed thus being sufficiently high to maintain at least the filtration zone of the slurry bed in a state of suspension.
- A process according to Claim 4, characterized in that the superficial gas velocity of gasses passing through the filtration zone is between 5 and 70 cm/s, based on the filtration zone open cross-sectional area.
- A process according to Claim 4 or Claim 5, characterized in that a plurality of the filtering media, arranged in banks, are provided, each filtering medium being provided by an elongate filter element mounted in the vessel and comprising the filtering medium which is in cylindrical form and a filtrate outlet for withdrawing liquid product at one end thereof, with the passage of the liquid product through the filtering elements being effected by applying a pressure differential of up to 8 bar across the filtering media of the elements and any cake build-up thereon.
- A process according to Claim 6, characterized in that the pressure differential is effected by withdrawing the liquid product into a rundown vessel which is at a lower pressure than the reactor vessel, with the filtrate outlets of the filter elements being connected to the rundown vessel by means of liquid product conduits, with the flushing fluid being liquid product and/or gaseous product, and with the backflushing including urging the flushing fluid through the conduits and filter elements in a direction opposite to the direction of normal liquid product flow during filtration.
- A process according to Claim 7, characterized in that the backflushing is effected in pulse-like fashion, with an initial pulse of flushing liquid product and/or gaseous product, followed by at least one further pulse of flushing liquid product and/or gaseous product.
- A process according to Claim 8, characterized in that each backflushing pulse comprises initiating flow of flushing fluid rapidly; and backflushing the elements rapidly with a volume of the flushing fluid.
- A process according to claim 9, characterized in that the backflushing includes, during the initial pulse, forcing residual liquid product in the liquid product conduits through the filter elements in the second direction, by means of pressurized gaseous product.
- A process according to claim 10 characterized in that, during the initial backflushing pulse, the residual liquid product is forced through a restriction orifice in the conduit below each filter element.
- A process according to any one of claims 7 to 11 inclusive, characterized in that the pressure differential across the filtering media and any filter cake build-up thereon during backflushing is up to 10 bar depending on the properties of the filter cake.
- A process according to any one of claims 7 to 12 inclusive, characterized in that the waiting period is between 15 and 60 minutes.
- A process according to any one of the preceding claims, characterized in that the backflushing of the filtering medium is effected by passing a flushing liquid through the filtering medium.
- An installation for producing liquid and, optionally, gaseous products from gaseous reactants, characterized in that the installation comprisesa reactor vessel having a slurry bed zone which, in use, will contain a slurry bed of solid particles suspended in a suspension liquid;a gas inlet in the vessel at a low level within the slurry bed zone, for introducing gaseous reactants into the vessel;a gas outlet in the vessel above the slurry bed zone, for withdrawing unreacted gaseous reactants and, when present, gaseous products from the vessel;a plurality of filter elements mounted in a filtration zone located within the slurry bed zone, each filtering element providing a filtering medium;liquid displacement means for displacing liquid product through the filtering medium in a first direction, while solid particles build up as a cake on the filtering medium; andbackflushing means for passing a flushing fluid through the filtering medium in a second direction, opposite to the first direction, from time to time, thereby to dislodge the cake from the filtering medium.
- An installation according to Claim 15, characterized in that the filter elements are of elongate form, with the filtering medium being of cylindrical form and enclosing a filtrate collecting zone, and with a filtrate outlet for withdrawing liquid product, being provided at one end thereof.
- An installation according to Claim 16, characterized in that the filter elements are located vertically with their filtrate outlets directed downwardly, and are arranged in a plurality of banks each comprising a number of the filter elements.
- An installation according to Claim 17, characterized in that it includes a primary conduit leading from the filtrate outlet of each filter element, a secondary conduit into which the primary conduits of all the filter elements of one of the banks of filter elements tie, and a tertiary conduit into which all the secondary conduits tie and which leads to a rundown vessel.
- An installation according to Claim 18, characterized in that the liquid product conduits and rundown vessel form part of the backflushing means, with the rundown vessel then also constituting a flushing fluid vessel and the liquid product conduits also constituting flushing fluid conduits.
- An installation according to Claim 18, characterized in that it includes a flushing fluid vessel and a flushing fluid conduit leading from the flushing fluid vessel to the secondary conduits.
- An installation according to Claim 19 or Claim 20, characterized in that the backflushing means includes at least one quick opening valve for effecting backflushing in pulse-like fashion, in one of the flushing fluid conduits; and pressurizing means for pressurizing the flushing fluid vessel so that backflushing is effected by pressurizing the flushing fluid vessel, with the vessel containing some flushing fluid, and then actuating the quick opening valve until the desired volume of flushing fluid gas has passed through the filter elements of one of the banks of the filter elements in the second direction.
- An installation according to any one of Claims 18 to 21 inclusive, characterized in that the backflushing means includes a restriction orifice in the primary conduit of each filter element.
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ZA930588 | 1993-01-27 | ||
ZA93588 | 1993-01-27 |
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EP (1) | EP0609079B1 (en) |
JP (1) | JP3514503B2 (en) |
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FR873645A (en) * | 1940-07-05 | 1942-07-15 | Int Koolwaterstoffen Synthese | Process for increasing in the synthesis from carbon monoxide and hydrogen the yield of boiling hydrocarbons in the zone of diesel oils |
US2540706A (en) * | 1947-05-22 | 1951-02-06 | Texas Co | Process and apparatus for effecting catalytic reactions |
US2671103A (en) * | 1949-10-28 | 1954-03-02 | Rheinpreussen Ag | Catalytic hydrogenation of carbon monoxide in liquid suspensions of catalyst |
FR2494682A1 (en) * | 1980-11-25 | 1982-05-28 | Inst Francais Du Petrole | PROCESS FOR IMPLEMENTING VERY EXOTHERMIC REACTIONS |
DE3149273C2 (en) * | 1981-10-20 | 1986-10-16 | Klöckner CRA Technologie GmbH, 4100 Duisburg | Process for the production of gasoline-like hydrocarbons |
US4472534A (en) * | 1982-07-23 | 1984-09-18 | Shell Oil Company | Slurry phase syngas process |
JPS60147228A (en) * | 1984-01-12 | 1985-08-03 | Mitsubishi Heavy Ind Ltd | Three-phase fluidized reaction apparatus |
US5324335A (en) * | 1986-05-08 | 1994-06-28 | Rentech, Inc. | Process for the production of hydrocarbons |
DD274981A1 (en) * | 1986-06-05 | 1990-01-10 | Leuna Werke Veb | REACTOR WITH INTERNAL FILTER FOR CONTINUOUS SUSPENSION PROCESSES |
US4801573A (en) * | 1987-10-23 | 1989-01-31 | 501 Den Norske Stats Oljeslenskap A.S. | Catalyst for production of hydrocarbons |
US5070064A (en) * | 1989-08-07 | 1991-12-03 | Exxon Research And Engineering Company | Catalyst pretreatment method |
CA2037250A1 (en) * | 1990-03-07 | 1991-09-08 | Rocco A. Fiato | Slurry fischer-tropsch hydrocarbon synthesis with high surface area reduced carbided iron/catalysts |
CA2038774C (en) * | 1990-04-04 | 2001-09-25 | Eric Herbolzheimer | Slurry bubble column |
CA2038773C (en) * | 1990-04-04 | 1999-06-08 | Kym B. Arcuri | Slurry fischer-tropsch process with co/ti02 catalyst |
DE4106536A1 (en) * | 1991-03-01 | 1992-09-03 | Degussa | THERMALLY-PAINTED ZIRCONYLICATE, METHOD FOR THE PRODUCTION AND USE THEREOF |
GB9203959D0 (en) * | 1992-02-25 | 1992-04-08 | Norske Stats Oljeselskap | Method of conducting catalytic converter multi-phase reaction |
CA2105940C (en) * | 1992-10-05 | 2001-12-25 | Robert M. Koros | Bubble column, tube side slurry process and apparatus |
US5599849A (en) * | 1993-01-27 | 1997-02-04 | Sasol Chemical Industries (Proprietary) Limited | Process for producing liquid and, optionally, gaseous products from gaseous reactants |
GB2281224B (en) * | 1993-08-24 | 1998-02-11 | Norske Stats Oljeselskap | Solid/liquid slurry treatment apparatus and catalytic multi-phase reactor |
-
1994
- 1994-01-25 US US08/187,189 patent/US5599849A/en not_active Expired - Lifetime
- 1994-01-25 NZ NZ250750A patent/NZ250750A/en unknown
- 1994-01-26 CA CA002114275A patent/CA2114275C/en not_active Expired - Lifetime
- 1994-01-26 NO NO940271A patent/NO302219B1/en not_active IP Right Cessation
- 1994-01-26 MY MYPI94000204A patent/MY113269A/en unknown
- 1994-01-27 ZA ZA94582A patent/ZA94582B/en unknown
- 1994-01-27 AU AU54741/94A patent/AU660573B2/en not_active Expired
- 1994-01-27 AT AT94300600T patent/ATE168583T1/en active
- 1994-01-27 DE DE69411767T patent/DE69411767T2/en not_active Expired - Lifetime
- 1994-01-27 EP EP94300600A patent/EP0609079B1/en not_active Expired - Lifetime
- 1994-01-27 JP JP03748794A patent/JP3514503B2/en not_active Expired - Fee Related
-
1996
- 1996-09-27 US US08/719,707 patent/US5844006A/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6803029B2 (en) | 2002-02-22 | 2004-10-12 | Chevron U.S.A. Inc. | Process for reducing metal catalyzed coke formation in hydrocarbon processing |
US8298828B2 (en) | 2003-06-20 | 2012-10-30 | Roche Diagnostics Operations, Inc. | System and method for determining the concentration of an analyte in a sample fluid |
US8663442B2 (en) | 2003-06-20 | 2014-03-04 | Roche Diagnostics Operations, Inc. | System and method for analyte measurement using dose sufficiency electrodes |
EP1927647A1 (en) | 2006-11-30 | 2008-06-04 | Chevron Oronite Company LLC | Traction coefficient reducing lubricating oil composition |
Also Published As
Publication number | Publication date |
---|---|
JP3514503B2 (en) | 2004-03-31 |
EP0609079A1 (en) | 1994-08-03 |
MY113269A (en) | 2002-01-31 |
AU5474194A (en) | 1994-08-04 |
CA2114275C (en) | 2004-05-25 |
US5844006A (en) | 1998-12-01 |
DE69411767D1 (en) | 1998-08-27 |
AU660573B2 (en) | 1995-06-29 |
NO940271L (en) | 1994-07-28 |
US5599849A (en) | 1997-02-04 |
JPH07800A (en) | 1995-01-06 |
ZA94582B (en) | 1994-09-13 |
CA2114275A1 (en) | 1994-07-28 |
NO940271D0 (en) | 1994-01-26 |
NZ250750A (en) | 1995-02-24 |
ATE168583T1 (en) | 1998-08-15 |
NO302219B1 (en) | 1998-02-09 |
DE69411767T2 (en) | 1998-12-03 |
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